CN102730863B - Method for treating light oil-leaking circulating water - Google Patents
Method for treating light oil-leaking circulating water Download PDFInfo
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- CN102730863B CN102730863B CN201110082711.4A CN201110082711A CN102730863B CN 102730863 B CN102730863 B CN 102730863B CN 201110082711 A CN201110082711 A CN 201110082711A CN 102730863 B CN102730863 B CN 102730863B
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Abstract
The invention provides a method for treating light oil-leaking circulating water, comprising the following steps of: a) adding an oxidation type bactericide; b) adding a scale and corrosion inhibitor which comprises at least an organophosphonate acid, at least an organic carboxylic acid polymer, an optional copper corrosion inhibitor and optional zinc salt; and c) adding at least a long-chain alkyl aryl sulfonate surfactant. The method provided by the invention can be used to remove oil and peel off microbial slime from equipment of the circulating water system at a time without large-scale pollution discharge.
Description
Technical field
The present invention relates to a kind for the treatment of process of recirculated water, relate in particular to a kind of circulating water treatment method of leaking lightweight oil.
Background technology
The hydrocarbon mixture that boiling spread is about 50-350 DEG C generally made a general reference by lightweight oil.In petroleum refining industry, it can refer to light ends oil, also can refer to clean or white.The former comprises cut and the topses such as gasoline (or petroleum naphtha), pyrolysis gasoline, kerosene (or rocket engine fuel), solar oil (or atmospheric gas oil), raffinates oil, and they are mainly from devices such as crude distillation, catalytic cracking, thermally splitting, petroleum coking, hydrocracking and catalytic reforming; The latter is the oil product that light ends oil obtains after treating process.When there is material from leakage, lightweight oil easily and water generation emulsifying effect enter circulating water system, for the microorganism in system provides sufficient nutrient source, microorganism can be bred rapidly at short notice, produce large number of biological foundry loam, water body is turned black and fouls, it is attached in interchanger and heat transfer efficiency can be made to reduce rapidly, and corrosion-mitigation scale-inhibition medicament can not be played a role, cause serious underdeposit corrosion.Large chemical complex takes the treatment process of large excretion and large complement usually, namely first adds adhesive mud remover, a large amount of draining after peeling off, then adds corrosion inhibiting and descaling agent.The method consumes a large amount of fresh waters and produces the sewer of equivalent, wastes water treatment agent, and needs after blowdown again to improve cycles of concentration, brings trouble to operation.
Chinese patent application CN1193609A discloses in a kind of circulating water system and waits the cleaning prefilming agent of dirt for microorganism dirt in cleaning system, cleaning prefilming agent is made up of biological enzyme scavenging agent, biostats, inorganic salt complex agent and the conventional water quality stabilizer that is made up of inhibiter and dispersion agent, and wherein inorganic salt complex agent is made up of silicate, manganate, carbonate, orthophosphoric acid salt.Purging method is under the normal operating condition of circulating water regiment commander thermal load, biological enzyme scavenging agent, biostats, inorganic salt complex agent and conventional water quality stabilizer are joined in recirculated water by the certain concentration of always possessing the water yield respectively, and maintains this concentration 15-60 days.Chinese patent application CN1125697A discloses the using method of a kind of biological cleanser in circulating water system, adds in circulating water system by biological enzyme scavenging agent, and biological enzyme scavenging agent is fat hydrolase.Conventional water quality stabilizer can be added in circulating water system.The method is adopted by the oily waste degradation in recirculated water, leaked substance to be degraded.Its shortcoming is and employs expensive biological enzyme scavenging agent.
Summary of the invention
The object of the present invention is to provide a kind of circulating water treatment method of leaking lightweight oil.Use method of the present invention can carry out oil removing, peel off microorganism viscosity mud the equipment of circulating water system, can once complete, without the need to a large amount of blowdown.
To achieve the above object of the invention, the invention provides a kind of circulating water treatment method of leaking lightweight oil, it comprises the following steps:
A) oxidative bactericide is added;
B) add anti-incrustation corrosion inhibitor, described anti-incrustation corrosion inhibitor comprises at least one organic phospho acid, at least one organic carboxyl acid base polymer, optional copper material corrosion inhibitor and optional zinc salt;
C) at least one long-chain alkyl aryl sulfosalt surfactant is added.
Oxidative bactericide of the present invention is the sterilant that at least one is selected from chloride sterilant and brominated sterilant; Described chloride sterilant is preferably from chlorine, hypochlorous acid and salt thereof, dichloroisocyanuric acid sodium, TCCA (Trichloroisocyanuric acid), 1,3-bis-chloro-5, chloro-5, the 5-dimethyl hydantion of the bromo-3-of 5-dimethyl hydantion, 1-, wherein hypochlorite is more preferably from clorox, Losantin; Described brominated sterilant is more preferably from hypobromous acid and salt, organo bromine microbicide and bromine chloride, wherein hypobromite more preferably from sodium hypobromite and hypobromous acid calcium, organo bromine microbicide more preferably from 2,2-bis-bromo-3-aminopropan acid amides and chloro-5, the 5-dimethyl of the bromo-3-of 1-are for glycolylurea; Be most preferably 10-50mg/L relative to the effective concentration of pending aqueous solution total amount oxidative bactericide.
Method of the present invention comprises and in recirculated cooling water, adds regular oxidation type sterilant according to a conventional method, with the microorganism in controlled circulation cooling water system.Regular oxidation type sterilant, can the microorganism of effective controlled circulation cooling water system, prevents a large amount of generations of microorganism excess growth and foundry loam.
In anti-incrustation corrosion inhibitor of the present invention, organic phospho acid is selected from 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid (HEDP), Amino Trimethylene Phosphonic Acid (ATMP), 2-phosphonate group-1,2,4-butane tricarboxylate (PBTCA), hydroxyethylidene diphosphonic acid guanidine-acetic acid (HPAA), ethylene diamine tetra methylene phosphonic acid (EDTMP), diethylene triamine pentamethylene phosphonic (DETPMP), to two phosphono and sulfonics, glycine two methylenephosphonic acid, L-glutamic acid two methylenephosphonic acid, thionamic acid two methylenephosphonic acid, taurine two methylenephosphonic acid and polyether-based polyamino methylene phosphonic acid.
In anti-incrustation corrosion inhibitor of the present invention, organic carboxyl acid base polymer is selected from homopolymer, copolymer and terpolymer, preferably from poly aspartic acid, poly-epoxy succinic acid, polyacrylic acid, polymaleic anhydride, vinylformic acid/Propylene glycol monoacrylate multipolymer, vinylformic acid/Propylene glycol monoacrylate/methyl acrylate copolymer, toxilic acid (acid anhydride)/Styrene Sulfonic Acid Copolymer, vinylformic acid/Styrene Sulfonic Acid Copolymer, acrylate/Styrene Sulfonic Acid Copolymer, toxilic acid (acid anhydride)/allyl sulphonic acid multipolymer, vinylformic acid/allyl sulphonic acid multipolymer, vinylformic acid/vinyl sulfonic acid multipolymer, vinylformic acid/2-methyl-2 '-acrylamido propane sulfonic acid multipolymer, acrylic acid/acrylamide/2-methyl-2 '-acrylamido propane sulfonic acid multipolymer, acrylic acid/esters/2-methyl-2 '-acrylamido propane sulfonic acid multipolymer, vinylformic acid/toxilic acid/2-methyl-2 '-acrylamido propane sulfonic acid multipolymer and vinylformic acid/2-acrylamido-2-methylpropanephosphonic acid/2-methyl-2 '-acrylamido propane sulfonic acid multipolymer.Wherein said acrylate is preferably from vinylformic acid C
1-8ester, more preferably from methyl acrylate, ethyl propenoate, Propylene glycol monoacrylate.
When using equipment made of copper in circulating water water system, anti-incrustation corrosion inhibitor of the present invention also contains heterogeneous ring compound as copper material corrosion inhibitor, is preferably methyl benzotriazazole, benzotriazole or mercaptobenzothiazole.
For the recirculated cooling water that corrodibility is stronger, its inhibition problem should be the major issue that will solve, when composite scale-inhibiting corrosion inhibitor is used for recirculated cooling water, also can containing zinc salt as inhibiter, and described zinc salt is zinc sulfate or zinc chloride.
Anti-incrustation corrosion inhibitor of the present invention relative to the effective concentration of each component of pending aqueous solution total amount is: organic phosphine 2-15mg/L, machine carboxylic-acid polymer concentration is 2-15mg/L, the effective concentration of copper material corrosion inhibitor is 0-1.5mg/L, is preferably 0.5-1.5mg/L, and the effective concentration of zinc salt is with Zn
2+count 0-3.0mg/L, be preferably 0.5-3.0mg/L.
Long-chain alkyl aryl sulfosalt surfactant of the present invention is preferably from long-chain alkyl benzene sulfonate; More preferably from C
12-C
18sodium alkyl benzene sulfonate; Most preferably from Sodium dodecylbenzene sulfonate, tetradecyl benzene sulfonic acid sodium salt and cetyl benzenesulfonic acid sodium.
The adding purpose of tensio-active agent is microorganism viscosity mud on peeling apparatus tube wall and prevents from again adhering to.Long-chain alkyl aryl sulfosalt surfactant of the present invention is 2-50mg/L relative to total effective concentration of pending aqueous solution total amount long-chain alkyl aryl sulfosalt surfactant.
Of the present invention b) described in step anti-incrustation corrosion inhibitor can add in the mode of single dose, also first can be mixed with composite scale-inhibiting corrosion inhibitor, then composite scale-inhibiting corrosion inhibitor is once added in recirculated water, preferably carry out in the mode of the latter.Using conventional procedures prepares composite scale-inhibiting corrosion inhibitor of the present invention, the reinforced order of each component is unimportant, such as organic phospho acid, organic carboxyl acid base polymer, zinc salt and copper material corrosion inhibitor and water can be mixed in predetermined ratio, required composite scale-inhibiting corrosion inhibitor can be obtained.In the preparation process of composite scale-inhibiting corrosion inhibitor, also can add a small amount of acid (as dilute sulphuric acid, dense or dilute hydrochloric acid etc.), to promote the dissolving of zinc salt, obtain the uniform solution of the composite scale-inhibiting corrosion inhibitor needing concentration as early as possible.
The addition step of lightweight oil circulating water treatment method of the present invention can be undertaken by a), b) and c) step successively, also can carry out a)-c by other arbitrary orders) step, these three steps can also be carried out simultaneously.
Method of the present invention is by adding oxidized form series bactericidal agent, long-chain alkyl aryl sulfosalt surfactant, can while control microorganism growth, microorganism viscosity mud in effective stripping exchanger tube wall, and prevent microorganism viscosity mud from again adhering to, be applied to together with composite scale-inhibiting corrosion inhibitor in recirculated cooling water, water treatment efficiency when circulating water system is leaked can be guaranteed, make system with low blowdown flow rate, comparatively high concentration multiple smooth running.Advantage of the present invention is simple to operate, without the need to the large excretion and large complement of water.Can be used for the online restoration methods after realizing circulating water system leakage lightweight oil.
Embodiment
The following examples will contribute to the present invention is described, but not limit to its scope.
Following embodiment 1-20 and comparative example 1-14 test raw water quality used is in table 1.
Raw water quality tested by table 1
Note: 1) pH is without unit, specific conductivity is μ s/cm, and its counit is mg/L, Ca
2+, total alkalinity, total hardness is all with CaCO
3meter, lower same; 2) Ca
2+represent calcium hardness, lower same.
The Reliable Evaluating Methods of Their Performance of the composite scale-inhibiting corrosion inhibitor prepared by following embodiment is as follows:
Corrosion inhibition: the corrosion inhibition of the following examples is all tested according to National Standard of the People's Republic of China GB/T 18175-2000 " the mensuration rotary hanging plate method of water conditioner corrosion inhibition ".By 20
#qualitative carbon steel test piece is fixed on lacing film instrument, puts into the test water being added with the scale inhibitor agent concentration added by embodiment and (table 1 is tested former water 1,2,3 and supplement Ca respectively
2+numerical value when cycles of concentration is 3,5,5 times separately to it with basicity, as test water), steady temperature 40 ± 1 DEG C, keeps rotating speed 75r/min to rotate 72h, and the weight of test piece before and after record test, calculates average corrosion rate.
Average corrosion rate calculation formula is:
F＝(C×ΔW)/(A×T×ρ)
C: computational constant, time in units of mm/a, C=8.76 × 10
7
Δ W: the corrosion weight loss (g) of test specimen
A: the area (cm of test specimen
2)
T: corrosion test time (h)
ρ: the density (kg/m of material for test
3)
Resistance calcium carbonate scale performance: the scale-inhibiting properties of the following examples is all tested according to National Standard of the People's Republic of China GB/T 16632-1996 " the mensuration tosca method of water conditioner scale-inhibiting properties ".Get test water and (supplement Ca respectively by testing former water 1,2,3 in table 1
2+numerical value when cycles of concentration is 3,5,5 times separately to it with basicity, as test water), add the scale inhibitor agent concentration added by embodiment, in sampling analysis water, remain Ca
2+concentration, make blank sample simultaneously, and calculate scale inhibition performance.
Scale inhibition performance=(C-C
0)/(C
1-C
0) × 100%
C: the rear Ca of test solution test adding water conditioner
2+concentration (mg/L)
C
0: with Ca after the blank test solution test of water conditioner
2+concentration (mg/L)
C
1: Ca in the test solution configured before test
2+concentration (mg/L)
The mensuration of heterotrophic bacterium: get test water sample, adopts former water 10 times of dilution technologies in sterilisable chamber, test water sample is diluted to suitable multiple, and is inoculated in culture dish by the water sample of corresponding extension rate.Then aseptic culture medium being poured in culture dish, mix with water sample, cultivating 72 ± 4h etc. being inverted after culture medium solidifying to be placed in the incubator of 29 ± 1 DEG C.After cultivation, take out culture dish, select those culture dish with 30-300 bacterium colony to count, colony number is multiplied by the heterotrophic bacterium number that corresponding dilution training number is this water sample.
Adhere to the mensuration of speed: be positioned on by test tube in the bypass of interchanger, take out test tube after off-test, after cleaning test tube outer wall, constant temperature drying, takes the heavy (W of band bur test tube
1).Then inboard wall of test tube bur is cleaned, dry, take the heavy (W of test tube
2), calculate and adhere to speed F '.
F’＝7.2×10
5×(W
1-W
2)/(A×t)
A: the area (cm of test specimen
2)
T: corrosion test time (h)
When measuring scale-inhibiting properties, following embodiment and comparative example use any test water quality all not adjust pHs; When measuring corrosion inhibition, when following embodiment and the water distribution 1 of comparative example use-testing, need adjust pH.
Embodiment 1
The preparation of anti-incrustation corrosion inhibitor: the Zinc Sulphate Heptahydrate of 8.8g is dissolved in 75.6 grams of water, be uniformly dissolved, add the HEDP that 8g concentration is 50%, shake up, add vinylformic acid/2-methyl-2 '-acrylamido propane sulfonic acid multipolymer (Limiting Viscosity when mass ratio of vinylformic acid and 2-methyl-2 '-acrylamido propane sulfonic acid is 7: 3,30 DEG C in multipolymer is 0.068dl/g) that 6.7g solid content is 30%, shake up, add 0.9g benzotriazole, shake up.
When adding in test water (being prepared by former water 3) by the scale inhibitor agent concentration of 100mg/L with the scale inhibitor agent solution prepared, HEDP in water, vinylformic acid/2-methyl-2 '-acrylamido propane sulfonic acid multipolymer, Zn
2+, benzotriazole effective concentration be respectively 4mg/L, 2mg/L, 2mg/L, 0.9mg/L.
In beaker, add 200mg pyrolysis gasoline during corrosion inhibition test, add 50mg pyrolysis gasoline during antisludging test in volumetric flask, then add Sodium dodecylbenzene sulfonate 48mg/L, test-results is in table 2.
Embodiment 2
The preparation of anti-incrustation corrosion inhibitor: by 10g concentration be 40% HPAA and 8g concentration be 50% PBTCA be dissolved in 46.5 grams of water, be uniformly dissolved, add the Zinc Sulphate Heptahydrate of 8.8g, shake up, add 26.7g solid content be 30% vinylformic acid/2-methyl-2 '-acrylamido propane sulfonic acid multipolymer (in multipolymer, the mass ratio of vinylformic acid and 2-methyl-2 '-acrylamido propane sulfonic acid is 7: 3, Limiting Viscosity when 30 DEG C is 0.068dl/g), shake up.
When adding in test water (being prepared by former water 3) by the scale inhibitor agent concentration of 100mg/L with the scale inhibitor agent solution prepared, HPAA, PBTCA in water, vinylformic acid/2-methyl-2 '-acrylamido propane sulfonic acid multipolymer, Zn
2+effective concentration be respectively 4mg/L, 4mg/L, 8mg/L, 2mg/L.
In beaker, add 200mg pyrolysis gasoline during corrosion inhibition test, add 50mg pyrolysis gasoline during antisludging test in volumetric flask, then add tetradecyl benzene sulfonic acid sodium salt 40mg/L, test-results is in table 2.
Embodiment 3
The preparation of anti-incrustation corrosion inhibitor: by 20g concentration be 50% PBTCA add in 46.7g water, shake up, add the polyacrylic acid (Limiting Viscosity when 30 DEG C is 0.071dl/g) that 33.3g solid content is 30%, shake up.
When adding in test water (being prepared by former water 2) by the scale inhibitor agent concentration of 100mg/L with the scale inhibitor agent solution prepared, in water, PBTCA, polyacrylic effective concentration are respectively 10mg/L, 10mg/L.
In beaker, add 200mg solar oil during corrosion inhibition test, add 50mg solar oil during antisludging test in volumetric flask, then add cetyl benzenesulfonic acid sodium 30mg/L, test-results is in table 2.
Embodiment 4
The preparation of anti-incrustation corrosion inhibitor: by 4g concentration be 50% be dissolved in 42g water to the DETPMP that two phosphono and sulfonics and 4g concentration are 50%, shake up, add 50g solid content be 30% vinylformic acid/Propylene glycol monoacrylate/methyl acrylate terpolymer (in multipolymer, the mass ratio of vinylformic acid and Propylene glycol monoacrylate, methyl acrylate is 3: 1: 1, Limiting Viscosity when 30 DEG C is 0.076dl/g), shake up.
When adding in the former water of test (being prepared by former water 2) by the scale inhibitor agent concentration of 100mg/L with the scale inhibitor agent solution prepared, in water, 2mg/L, 2mg/L, 15mg/L are respectively to the effective concentration of two phosphono and sulfonics, DETPMP, vinylformic acid/Propylene glycol monoacrylate/methyl acrylate copolymer.
In beaker, add 100mg pyrolysis gasoline during corrosion inhibition test, add 25mg pyrolysis gasoline during antisludging test in volumetric flask, then add Sodium dodecylbenzene sulfonate 10mg/L, test-results is in table 2.
Embodiment 5
The preparation of anti-incrustation corrosion inhibitor: by 26.7g solid content be 30% vinylformic acid/Propylene glycol monoacrylate multipolymer (in multipolymer, the mass ratio of vinylformic acid and Propylene glycol monoacrylate is 7: 3, Limiting Viscosity when 30 DEG C is 0.075dl/g) add in 48.8g water, be uniformly dissolved, add 16g concentration be 50% ATMP and 8g concentration be the EDTMP of 50%, shake up, add 0.7g methyl benzotriazazole again, shake up.
When adding in test water (being prepared by former water 2) by the scale inhibitor agent concentration of 100mg/L with the scale inhibitor agent solution prepared, in water, the effective concentration of ATMP, EDTMP, vinylformic acid/Propylene glycol monoacrylate multipolymer, methyl benzotriazazole is respectively 8mg/L, 4mg/L, 8mg/L, 0.7mg/L.
In beaker, add 40mg solar oil during corrosion inhibition test, add 10mg solar oil during antisludging test in volumetric flask, then add tetradecyl benzene sulfonic acid sodium salt 3mg/L, test-results is in table 2.
Embodiment 6
The preparation of anti-incrustation corrosion inhibitor: by 8g concentration be 50% PBTCA add in 48.7g water, be uniformly dissolved, add 13.3g solid content be 30% poly-epoxy succinic acid (Limiting Viscosity when 30 DEG C is 0.067dl/g) and 30g concentration be 30% vinylformic acid/2-methyl-2 '-acrylamido propane sulfonic acid multipolymer (in multipolymer, the mass ratio of vinylformic acid and 2-methyl-2 '-acrylamido propane sulfonic acid is 7: 3, Limiting Viscosity when 30 DEG C is 0.068dl/g), shake up.
When adding in test water (being prepared by former water 2) by the scale inhibitor agent concentration of 100mg/L with the scale inhibitor agent solution prepared, in water, the effective concentration of PBTCA, poly-epoxy succinic acid, vinylformic acid/2-methyl-2 '-acrylamido propane sulfonic acid multipolymer is respectively 4mg/L, 4mg/L, 9mg/L.
In beaker, add 200mg pyrolysis gasoline during corrosion inhibition test, add 50mg pyrolysis gasoline during antisludging test in volumetric flask, then add cetyl benzenesulfonic acid sodium 48mg/L, test-results is in table 2.
Embodiment 7
The preparation of anti-incrustation corrosion inhibitor: by 6g concentration be 50% add in 54.7g water to two phosphono and sulfonics, be uniformly dissolved, add glycine two methylenephosphonic acid that 6g solid content is 50%, shake up, add again 33.3g concentration be 30% vinylformic acid/Styrene Sulfonic Acid Copolymer (in multipolymer, the mass ratio of vinylformic acid and styrene sulfonic acid is 7: 3, Limiting Viscosity when 30 DEG C is 0.076dl/g), shake up.
When adding in test water (being prepared by former water 2) by the scale inhibitor agent concentration of 100mg/L with the scale inhibitor agent solution prepared, in water, 3mg/L, 3mg/L, 10mg/L are respectively to the effective concentration of two phosphono and sulfonics, glycine two methylenephosphonic acid, vinylformic acid/Styrene Sulfonic Acid Copolymer.
In beaker, add 200mg pyrolysis gasoline during corrosion inhibition test, add 50mg pyrolysis gasoline during antisludging test in volumetric flask, then add Sodium dodecylbenzene sulfonate 40mg/L, test-results is in table 2.
Embodiment 8
The preparation of anti-incrustation corrosion inhibitor: by 4g concentration be 50% L-glutamic acid two methylenephosphonic acid and 8g concentration be 50% thionamic acid two methylenephosphonic acid add in 58g water, be uniformly dissolved, add 16.7g solid content be 30% acrylate/Styrene Sulfonic Acid Copolymer (in multipolymer, the mass ratio of acrylate and styrene sulfonic acid is 7: 3, Limiting Viscosity when 30 DEG C is 0.067dl/g) and 13.3g concentration be 30% maleic anhydride/allyl sulphonic acid multipolymer (in multipolymer, the mass ratio of maleic anhydride and allyl sulphonic acid is 7: 3, Limiting Viscosity when 30 DEG C is 0.069dl/g), shake up.
When adding in test water (being prepared by former water 2) by the scale inhibitor agent concentration of 100mg/L with the scale inhibitor agent solution prepared, the effective concentration of water Glutamic Acid two methylenephosphonic acid, thionamic acid two methylenephosphonic acid, acrylate/Styrene Sulfonic Acid Copolymer, maleic anhydride/allyl sulphonic acid multipolymer is respectively 2mg/L, 4mg/L, 5mg/L, 4mg/L.
In beaker, add 200mg during corrosion inhibition test raffinate oil, add 50mg and raffinate oil during antisludging test in volumetric flask, tetradecyl benzene sulfonic acid sodium salt 30mg/L, test-results is in table 2.
Embodiment 9
The preparation of anti-incrustation corrosion inhibitor: by 4g concentration be 50% taurine two methylenephosphonic acid add in g water, be uniformly dissolved, add the polyether-based polyamino methylene phosphonic acid that 4g concentration is 50%, shake up, add again 13.3g solid content be 30% maleic anhydride/Styrene Sulfonic Acid Copolymer (in multipolymer, the mass ratio of maleic anhydride and styrene sulfonic acid is 7: 3, Limiting Viscosity when 30 DEG C is 0.065dl/g) and 13.3g concentration be 30% acrylic acid/acrylamide/2-methyl-2 '-acrylamido propane sulfonic acid multipolymer (vinylformic acid and acrylamide in multipolymer, the mass ratio of 2-methyl-2 '-acrylamido propane sulfonic acid is 3: 1: 1, Limiting Viscosity when 30 DEG C is 0.071dl/g), shake up.
When adding in test water (being prepared by former water 2) by the scale inhibitor agent concentration of 100mg/L with the scale inhibitor agent solution prepared, in water, the effective concentration of taurine two methylenephosphonic acid, polyether-based polyamino methylene phosphonic acid, maleic anhydride/Styrene Sulfonic Acid Copolymer, acrylic acid/acrylamide/2-methyl-2 '-acrylamido propane sulfonic acid multipolymer is respectively 2mg/L, 2mg/L, 4mg/L, 4mg/L.
In beaker, add 200mg pyrolysis gasoline during corrosion inhibition test, add 50mg pyrolysis gasoline during antisludging test in volumetric flask, then add cetyl benzenesulfonic acid sodium 20mg/L, test-results is in table 2.
Embodiment 10
The preparation of anti-incrustation corrosion inhibitor: by 4g concentration be 50% EDTMP add in 62g water, be uniformly dissolved, add-2 '-acrylamido propane sulfonic acid multipolymer acid of vinylformic acid/toxilic acid/2-methyl (vinylformic acid and toxilic acid in multipolymer that 20g solid content is 30%, the mass ratio of 2-methyl-2 '-acrylamido propane sulfonic acid is 3: 1: 1, Limiting Viscosity when 30 DEG C is 0.066dl/g), shake up, add the DETPMP that 4g concentration is 50%, shake up, add vinylformic acid/2-acrylamido-2-methylpropanephosphonic acid/2-methyl-2 '-acrylamido propane sulfonic acid multipolymer (vinylformic acid and 2-acrylamido-2-methylpropanephosphonic acid in multipolymer that 10g concentration is 30% again, the mass ratio of 2-methyl-2 '-acrylamido propane sulfonic acid is 3: 1: 1, Limiting Viscosity when 30 DEG C is 0.068dl/g), shake up.
When adding in test water (being prepared by former water 2) by the scale inhibitor agent concentration of 100mg/L with the scale inhibitor agent solution prepared, EDTMP, DETPMP in water, vinylformic acid/toxilic acid/2-methyl-2 '-acrylamido propane sulfonic acid multipolymer, vinylformic acid/2-acrylamido-2-methylpropanephosphonic acid/2-methyl-2 '-acrylamido propane sulfonic acid multipolymer+effective concentration be respectively 2mg/L, 2mg/L, 6mg/L, 3mg/L.
In beaker, add 200mg pyrolysis gasoline during corrosion inhibition test, add 50mg pyrolysis gasoline during antisludging test in volumetric flask, then add Sodium dodecylbenzene sulfonate 10mg/L, test-results is in table 2.
Embodiment 11
The preparation of anti-incrustation corrosion inhibitor: by 23.3g solid content be 30% toxilic acid/Styrene Sulfonic Acid Copolymer (in multipolymer, the mass ratio of toxilic acid and styrene sulfonic acid is 7: 3, Limiting Viscosity when 30 DEG C is 0.072dl/g) and 13.3g solid content be 30% vinylformic acid/Styrene Sulfonic Acid Copolymer (in multipolymer, the mass ratio of vinylformic acid and styrene sulfonic acid is 7: 3, Limiting Viscosity when 30 DEG C is 0.076dl/g) be dissolved in 41.5g water, be uniformly dissolved, by 7.5g concentration be 40% HPAA and 10g concentration be 50% L-glutamic acid two methylenephosphonic acid, be uniformly dissolved, add the Zinc Sulphate Heptahydrate of 4.4g, shake up.
When adding in test water (being prepared by former water 1) by the scale inhibitor agent concentration of 100mg/L with the scale inhibitor agent solution prepared, HPAA, L-glutamic acid two methylenephosphonic acid, toxilic acid/Styrene Sulfonic Acid Copolymer, vinylformic acid/Styrene Sulfonic Acid Copolymer, Zn in water
2+effective concentration be respectively 3mg/L, 5mg/L, 7mg/L, 4mg/L, 1mg/L.
In beaker, add 200mg during corrosion inhibition test raffinate oil, add 50mg and raffinate oil during antisludging test in volumetric flask, then add tetradecyl benzene sulfonic acid sodium salt 40mg/L, be 7.7 ± 0.2 by sulfuric acid adjust ph in process of the test, test-results is in table 2.
Embodiment 12
The preparation of anti-incrustation corrosion inhibitor: the Zinc Sulphate Heptahydrate of 8.8g is dissolved in 41.8 grams of water, be uniformly dissolved 8g concentration be 50% glycine two methylenephosphonic acid and 8g concentration be 50% thionamic acid two methylenephosphonic acid, be uniformly dissolved, add 16.7g solid content be 30% vinylformic acid/allyl sulphonic acid multipolymer (in multipolymer, the mass ratio of vinylformic acid and allyl sulphonic acid is 7: 3, Limiting Viscosity when 30 DEG C is 0.065dl/g) and 16.7g solid content be 30% vinylformic acid/vinyl sulfonic acid multipolymer (in multipolymer, the mass ratio of vinylformic acid and vinyl sulfonic acid is 7: 3, Limiting Viscosity when 30 DEG C is 0.069dl/g), shake up.
When adding in test water (being prepared by former water 1) by the scale inhibitor agent concentration of 100mg/L with the scale inhibitor agent solution prepared, glycine two methylenephosphonic acid, thionamic acid two methylenephosphonic acid, vinylformic acid/allyl sulphonic acid multipolymer, vinylformic acid/vinyl sulfonic acid multipolymer, Zn in water
2+effective concentration be respectively 4mg/L, 4mg/L, 5mg/L, 5mg/L, 2mg/L.
In beaker, add 200mg pyrolysis gasoline during corrosion inhibition test, add 50mg pyrolysis gasoline during antisludging test in volumetric flask, then add cetyl benzenesulfonic acid sodium 30mg/L, be 7.7 ± 0.2 by sulfuric acid adjust ph in process of the test, test-results is in table 2.
Embodiment 13
The preparation of anti-incrustation corrosion inhibitor: the Zinc Sulphate Heptahydrate of 13.2g is dissolved in 6.8 grams of water, be uniformly dissolved 14g concentration be 50% taurine two methylenephosphonic acid and 16g concentration be 50% polyether-based polyamino methylene phosphonic acid, be uniformly dissolved, add vinylformic acid/toxilic acid/2-methyl-2 '-acrylamido propane sulfonic acid multipolymer (vinylformic acid and toxilic acid in multipolymer that 33.3g solid content is 30%, the mass ratio of 2-methyl-2 '-acrylamido propane sulfonic acid is 3: 1: 1, Limiting Viscosity when 30 DEG C is 0.066dl/g) and 16.7g solid content be 30% polymaleic anhydride (Limiting Viscosity when 30 DEG C is 0.074dl/g), shake up.
When adding in test water (being prepared by former water 1) by the scale inhibitor agent concentration of 100mg/L with the scale inhibitor agent solution prepared, taurine two methylenephosphonic acid in water, polyether-based polyamino methylene phosphonic acid, vinylformic acid/toxilic acid/2-methyl-2 '-acrylamido propane sulfonic acid multipolymer, polymaleic anhydride, Zn
2+effective concentration be respectively 7mg/L, 8mg/L, 10mg/L, 5mg/L, 3mg/L.
In beaker, add 100mg pyrolysis gasoline during corrosion inhibition test, add 25mg pyrolysis gasoline during antisludging test in volumetric flask, then add Sodium dodecylbenzene sulfonate 10mg/L, be 7.7 ± 0.2 by sulfuric acid adjust ph in process of the test, test-results is in table 2.
Embodiment 14
The preparation of anti-incrustation corrosion inhibitor: the Zinc Sulphate Heptahydrate of 8.8g is dissolved in 36.2g water, be uniformly dissolved 8g concentration be 50% HEDP and 8g concentration be the PBTCA of 50%, be uniformly dissolved, add 26.7g solid content be 30% poly aspartic acid (Limiting Viscosity when 30 DEG C is 0.067dl/g) and 13.3g solid content be 30% vinylformic acid/2-methyl-2 '-acrylamido propane sulfonic acid multipolymer (in multipolymer, the mass ratio of vinylformic acid and 2-methyl-2 '-acrylamido propane sulfonic acid is 7: 3, Limiting Viscosity when 30 DEG C is 0.068dl/g), shake up, add 0.8g mercaptobenzothiazole again, shake up.
When adding in test water (being prepared by former water 1) by the scale inhibitor agent concentration of 100mg/L with the scale inhibitor agent solution prepared, HEDP, PBTCA in water, poly aspartic acid, vinylformic acid/2-methyl-2 '-acrylamido propane sulfonic acid multipolymer, Zn
2+, mercaptobenzothiazole effective concentration be respectively 4mg/L, 4mg/L, 8mg/L, 4mg/L, 2mg/L, 0.8mg/L.
In beaker, add 40mg pyrolysis gasoline during corrosion inhibition test, add 10mg pyrolysis gasoline during antisludging test in volumetric flask, then add tetradecyl benzene sulfonic acid sodium salt 3mg/L, be 7.7 ± 0.2 by sulfuric acid adjust ph in process of the test, test-results is in table 2.
Comparative example 1
Test is except not adding except Sodium dodecylbenzene sulfonate, and test conditions and testing sequence are with embodiment 1, and test-results is in table 2.
Comparative example 2
Test is not except adding tetradecyl benzene sulfonic acid sodium salt, and test conditions and testing sequence are with embodiment 2, and test-results is in table 2.
Comparative example 3
Test is not except adding cetyl benzenesulfonic acid sodium, and test conditions and testing sequence are with embodiment 3, and test-results is in table 2.
Comparative example 4
Test is except not adding except Sodium dodecylbenzene sulfonate, and test conditions and testing sequence are with embodiment 4, and test-results is in table 2.
Comparative example 5
Test is not except adding tetradecyl benzene sulfonic acid sodium salt, and test conditions and testing sequence are with embodiment 5, and test-results is in table 2.
Comparative example 6
Test is not except adding cetyl benzenesulfonic acid sodium, and test conditions and testing sequence are with embodiment 6, and test-results is in table 2.
Comparative example 7
Test is except not adding except Sodium dodecylbenzene sulfonate, and test conditions and testing sequence are with embodiment 7, and test-results is in table 2.
Comparative example 8
Test is not except adding tetradecyl benzene sulfonic acid sodium salt, and test conditions and testing sequence are with embodiment 8, and test-results is in table 2.
Comparative example 9
Test is not except adding cetyl benzenesulfonic acid sodium, and test conditions and testing sequence are with embodiment 9, and test-results is in table 2.
Comparative example 10
Test is except not adding except Sodium dodecylbenzene sulfonate, and test conditions and testing sequence are with embodiment 10, and test-results is in table 2.
Comparative example 11
Test is not except adding tetradecyl benzene sulfonic acid sodium salt, and test conditions and testing sequence are with embodiment 11, and test-results is in table 2.
Comparative example 12
Test is not except adding cetyl benzenesulfonic acid sodium, and test conditions and testing sequence are with embodiment 12, and test-results is in table 2.
Comparative example 13
Test is except not adding except Sodium dodecylbenzene sulfonate, and test conditions and testing sequence are with embodiment 13, and test-results is in table 2.
Comparative example 14
Test is not except adding tetradecyl benzene sulfonic acid sodium salt, and test conditions and testing sequence are with embodiment 14, and test-results is in table 2.
Table 2 embodiment corrosion-mitigation scale-inhibition result
Note: the corrosion inhibition test of embodiment 1,5,10 all hangs with copper sheet, and its erosion rate is 0.001mm/a.
Data as can be seen from above-described embodiment and comparative example: adopt method process of the present invention containing when leaking the high, medium and low hardness water of lightweight oil, the inhibition the adding of Determination of Polyoxyethylene Non-ionic Surfactants not affecting anti-incrustation corrosion inhibitor and resistance calcium carbonate scale performance, and can effectively peel adhesion in the lightweight oil of equipment surface.
In order to simulated field, carried out dynamic analog test by the test method described in People's Republic of China (PRC) chemical industry standard HG/T2160-91, following embodiment 15 ~ 20 is dynamic simulation experiment.
Embodiment 15
The preparation of anti-incrustation corrosion inhibitor: the Zinc Sulphate Heptahydrate of 8.8g is dissolved in 74.5 grams of water, be uniformly dissolved, add the HEDP that 10g concentration is 50%, shake up, add 6.7g solid content be 30% vinylformic acid/2-methyl-2 '-acrylamido propane sulfonic acid multipolymer (in multipolymer, the mass ratio of vinylformic acid and 2-methyl-2 '-acrylamido propane sulfonic acid is 7: 3, Limiting Viscosity when 30 DEG C is 0.065dl/g), shake up.
Controling parameters is as follows:
Test water quality: the former water 3 of table 1
Calcium hardness+total alkali angle value: A tower 250 ± 50mg/L, B tower 250 ± 50mg/L
Flow velocity: 1.0m/s
Temperature in: 32 ± 1 DEG C
PH is uncomfortable
The temperature difference: 10 DEG C
Anti-incrustation corrosion inhibitor dosage is as follows:
A tower: containing pyrolysis gasoline 100mg/L in the water in A tower, add in test water with the scale inhibitor agent concentration of the scale inhibitor agent solution prepared by 100mg/L, the concentration of each component in water is made to be: HEDP 5mg/L, vinylformic acid/2-methyl-2 '-acrylamido propane sulfonic acid multipolymer 2mg/L, the effective concentration of zinc salt is with Zn
2+count 2mg/L, then add Sodium dodecylbenzene sulfonate 20mg/L and TCCA (Trichloroisocyanuric acid) 20mg/L.Test-results is in table 3.
B tower: test except not adding except Sodium dodecylbenzene sulfonate, test conditions and testing sequence are with A tower.Test-results is in table 3, table 4.
Embodiment 16
The preparation of anti-incrustation corrosion inhibitor: by 20g concentration be 50% PBTCA be dissolved in 50 grams of water, shake up, add 10g solid content be 30% acrylic acid/acrylamide/2-methyl-2 '-acrylamido propane sulfonic acid multipolymer (in multipolymer, the mass ratio of vinylformic acid and acrylamide, 2-methyl-2 '-acrylamido propane sulfonic acid multipolymer is 3: 1: 1, Limiting Viscosity when 30 DEG C is 0.071dl/g) and 20g solid content be 30% polymaleic anhydride (Limiting Viscosity when 30 DEG C is 0.068dl/g), shake up.
Controling parameters is as follows:
Test water quality: the former water 2 of table 1
Calcium hardness+total alkali angle value: A tower 1000 ± 50mg/L, B tower 1000 ± 50mg/L
Flow velocity: 1.0m/s
Temperature in: 32 ± 1 DEG C
PH is uncomfortable
The temperature difference: 10 DEG C
Anti-incrustation corrosion inhibitor dosage is as follows:
A tower: containing pyrolysis gasoline 100mg/L in the water in A tower, add in test water with the scale inhibitor agent concentration of the scale inhibitor agent solution prepared by 100mg/L, the concentration of each component in water is made to be: PBTCA 10mg/L, acrylic acid/acrylamide/2-methyl-2 '-acrylamido propane sulfonic acid multipolymer 3mg/L, polymaleic anhydride 6mg/L, add chloro-5, the 5-dimethyl hydantion 25mg/L of tetradecyl benzene sulfonic acid sodium salt 25mg/L and 1,3-bis-again.
B tower: test except not adding tetradecyl benzene sulfonic acid sodium salt, test conditions and testing sequence are with A tower.Test-results is in table 3, table 4.
Embodiment 17
The preparation of anti-incrustation corrosion inhibitor: by 4g concentration be 50% Amino Trimethylene Phosphonic Acid and 10g concentration be 50% polyether-based polyamino methylene phosphonic acid be dissolved in 56 grams of water, shake up, add 10g solid content be 30% vinylformic acid/Styrene Sulfonic Acid Copolymer (in multipolymer, the mass ratio of vinylformic acid and styrene sulfonic acid is 7: 3, Limiting Viscosity when 30 DEG C is 0.067dl/g) and 20g solid content be 30% vinylformic acid/vinyl sulfonic acid multipolymer (in multipolymer, the mass ratio of vinylformic acid and vinyl sulfonic acid multipolymer is 7: 3, Limiting Viscosity when 30 DEG C is 0.072dl/g), shake up.
Controling parameters is as follows:
Test water quality: the former water 2 of table 1
Calcium hardness+total alkali angle value: 1000 ± 50mg/L
Flow velocity: 1.0m/s
Temperature in: 32 ± 1 DEG C
PH is uncomfortable
The temperature difference: 10 DEG C
Anti-incrustation corrosion inhibitor dosage is as follows:
A tower: containing the 100mg/L that raffinates oil in the water in A tower, add in test water with the scale inhibitor agent concentration of the scale inhibitor agent solution prepared by 100mg/L, the concentration of each component in water is made to be: Amino Trimethylene Phosphonic Acid 2mg/L, polyether-based polyamino methylene phosphonic acid 5mg/L, vinylformic acid/Styrene Sulfonic Acid Copolymer 3mg/L, vinylformic acid/vinyl sulfonic acid multipolymer 6mg/L, then add cetyl benzenesulfonic acid sodium 15mg/L and dichloroisocyanuric acid sodium 30mg/L.Test-results is in table 3, table 4.
Embodiment 18
The preparation of anti-incrustation corrosion inhibitor: will be dissolved in 54 grams of water, be uniformly dissolved, add 10g concentration be 50% ATMP and 6g concentration be 50% to two phosphono and sulfonics, shake up, add 30g solid content be 30% maleic anhydride/allyl sulphonic acid multipolymer (in multipolymer, the mass ratio of maleic anhydride and allyl sulphonic acid is 7: 3, Limiting Viscosity when 30 DEG C is 0.076dl/g), shake up.
Controling parameters is as follows:
Test water quality: the former water 2 of table 1
Calcium hardness+total alkali angle value: 1000 ± 50mg/L
Flow velocity: 1.0m/s
Temperature in: 32 ± 1 DEG C
The temperature difference: 10 DEG C
Anti-incrustation corrosion inhibitor dosage is as follows:
A tower: containing solar oil 100mg/L in the water in A tower, add in test water with the scale inhibitor agent concentration of the scale inhibitor agent solution prepared by 100mg/L, the concentration of each component in water is made to be: ATMP 5mg/L, to two phosphono and sulfonic 3mg/L, maleic anhydride/allyl sulphonic acid multipolymer 9mg/L, add Sodium dodecylbenzene sulfonate 30mg/L and 2,2-bis-bromo-3-aminopropan acid amides 35mg/L again.Test-results is in table 3, table 4.
Embodiment 19
The preparation of anti-incrustation corrosion inhibitor:, by 6g concentration be 50% EDTMP and 6g concentration be 50% DETPMP be dissolved in 61.3 grams of water, shake up, add the polymaleic anhydride (Limiting Viscosity when 30 DEG C is 0.058dl/g) that 26.7g solid content is 30%, shake up.
Controling parameters is as follows:
Test water quality: the former water 2 of table 1
Calcium hardness+total alkali angle value: 1000 ± 50mg/L
Flow velocity: 1.0m/s
Temperature in: 32 ± 1 DEG C
PH is uncomfortable
The temperature difference: 10 DEG C
Anti-incrustation corrosion inhibitor dosage is as follows:
A tower: containing pyrolysis gasoline 100mg/L in the water in A tower, add in test water with the scale inhibitor agent concentration of the scale inhibitor agent solution prepared by 100mg/L, the concentration of each component in water is made to be: EDTMP 3mg/L, DETPMP 3mg/L, polymaleic anhydride concentration is 8mg/L, add chloro-5, the 5-dimethyl of the bromo-3-of tetradecyl benzene sulfonic acid sodium salt 25mg/L and 1-again for glycolylurea 40mg/L.Test-results is in table 3, table 4.
Embodiment 20
The preparation of anti-incrustation corrosion inhibitor: the Zinc Sulphate Heptahydrate of 13.2g is dissolved in 37.5 grams of water, be uniformly dissolved, add 8g concentration be 50% HEDP and 8g concentration be the PBTCA of 50%, shake up, add the poly-epoxy succinic acid (Limiting Viscosity when 30 DEG C is 0.063dl/g) that 33.3g solid content is 30%, shake up.
Controling parameters is as follows:
Test water quality: the former water 1 of table 1
Calcium hardness value: A tower 750 ± 50mg/L, B tower 750 ± 50mg/L
Flow velocity: 1.0m/s
Temperature in: 32 ± 1 DEG C
pH 7.7±0.2
The temperature difference: 10 DEG C
Anti-incrustation corrosion inhibitor dosage is as follows:
A tower: containing pyrolysis gasoline 100mg/L in the water in A tower, add in test water with the scale inhibitor agent concentration of the scale inhibitor agent solution prepared by 100mg/L, the concentration of each component in water is made to be: HEDP 4mg/L, PBTCA 4mg/L, poly-epoxy succinic acid concentration is 10mg/L, and the effective concentration of zinc salt is with Zn
2+count 3mg/L, then add cetyl benzenesulfonic acid sodium 15mg/L and hypobromous acid 45mg/L.Test-results is in table 3.
B tower: test except not adding cetyl benzenesulfonic acid sodium, test conditions and testing sequence are with A tower.Test-results is in table 3, table 4.
Table 3 dynamic analog test test tube result *
* the test carried out in the B tower in embodiment is simultaneous test.
Table 4 heterotrophic bacterium monitoring result *
* the test carried out in the B tower in embodiment is simultaneous test.
Specify in standard GB/T 50050-95 " Code for design of industrial recirculating cooling water treatment " 3.1.6, the corrosion speed of the carbon steel tube wall of open type system is less than or equal to 0.125mm/a; In " water coolant analysis and the test method " of production department of China PetroChemical Corporation and development division establishment, " the small-sized experimental analogic method of testing laboratory " specifies that the corrosion speed of carbon steel is " very well " level at 0-0.028mm/a, being " good " level between 0.028-0.056mm/a, is " can allow " level at 0.056-0.070mm/a; Adhesion speed is " very well " level at 0-6mcm, and being " good " level at 6-15mcm, is " can allow " level at 15-20mcm.Heterotrophic bacterium controls 10
5below lower to qualified.
As can be seen here, under the various condition of water quality that the circulating water treatment method applying leakage lightweight oil of the present invention is 100mg/L in pyrolysis gasoline concentration, prevent the effect of microorganism adhering and local corrosion fine, and effectively can control the microorganism containing leaking in the recirculated cooling water of oil product by the dosage controlling sterilant, the erosion rate of test tube is 0.025-0.039mm/a, reach China Petrochemical Industry's " very well " level and " good level " standard, adhere to speed 7.7-13.6mcm, reach " good level " standard, be better than comparative example and do not add the inhibition of tensio-active agent in senior middle school's low-hardness water and scale inhibition effect.
Claims (24)
1. leak a circulating water treatment method for lightweight oil, it comprises the following steps: a) add oxidative bactericide; B) add anti-incrustation corrosion inhibitor, described anti-incrustation corrosion inhibitor comprises at least one organic phospho acid, at least one organic carboxyl acid base polymer, optional copper material corrosion inhibitor and optional zinc salt; C) at least one long-chain alkyl aryl sulfonate surfactant is added.
2. circulating water treatment method according to claim 1, is characterized in that described oxidative bactericide is the sterilant that at least one is selected from chloride sterilant and brominated sterilant.
3. circulating water treatment method according to claim 2, it is characterized in that described chloride sterilant is selected from chlorine, hypochlorous acid and salt thereof, dichloroisocyanuric acid sodium, TCCA (Trichloroisocyanuric acid), 1, chloro-5, the 5-dimethyl hydantion of 3-bis-, chloro-5, the 5-dimethyl hydantion of the bromo-3-of 1-; Described brominated sterilant is selected from hypobromous acid and salt, organo bromine microbicide and bromine chloride.
4. circulating water treatment method according to claim 3, is characterized in that described hypochlorite is selected from clorox, Losantin; Described hypobromite is selected from sodium hypobromite and hypobromous acid calcium; Described organo bromine microbicide is selected from 2,2-bis-bromo-3-time aminopropan acid amides and chloro-5, the 5-dimethyl of the bromo-3-of 1-for glycolylurea.
5. circulating water treatment method according to claim 1, is characterized in that relative to the effective concentration of pending aqueous solution total amount oxidative bactericide be 10-50mg/L.
6. the circulating water treatment method according to any one of claim 1-5, it is characterized in that described organic phospho acid is selected from 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid, Amino Trimethylene Phosphonic Acid, 2-phosphonate group-1,2,4-butane tricarboxylate, hydroxyethylidene diphosphonic acid guanidine-acetic acid, ethylene diamine tetra methylene phosphonic acid, diethylene triamine pentamethylene phosphonic, to two phosphono and sulfonics, glycine two methylenephosphonic acid, L-glutamic acid two methylenephosphonic acid, thionamic acid two methylenephosphonic acid, taurine two methylenephosphonic acid and polyether-based polyamino methylene phosphonic acid.
7. the circulating water treatment method according to any one of claim 1-5, is characterized in that described organic carboxyl acid base polymer is selected from homopolymer, copolymer and terpolymer.
8. circulating water treatment method according to claim 7, is characterized in that described organic carboxyl acid base polymer is selected from poly aspartic acid, poly-epoxy succinic acid, polyacrylic acid, polymaleic anhydride, vinylformic acid/Propylene glycol monoacrylate multipolymer, vinylformic acid/Propylene glycol monoacrylate/methyl acrylate copolymer, toxilic acid/Styrene Sulfonic Acid Copolymer, maleic anhydride/Styrene Sulfonic Acid Copolymer, vinylformic acid/Styrene Sulfonic Acid Copolymer, acrylate/Styrene Sulfonic Acid Copolymer, toxilic acid/allyl sulphonic acid multipolymer, maleic anhydride/allyl sulphonic acid multipolymer, vinylformic acid/allyl sulphonic acid multipolymer, vinylformic acid/vinyl sulfonic acid multipolymer, vinylformic acid/2-methyl-2'-acrylamido propane sulfonic acid multipolymer, acrylic acid/acrylamide/2-methyl-2'-acrylamido propane sulfonic acid multipolymer, acrylic acid/esters/2-methyl-2'-acrylamido propane sulfonic acid multipolymer, vinylformic acid/toxilic acid/2-methyl-2'-acrylamido propane sulfonic acid multipolymer and vinylformic acid/2-acrylamido-2-methylpropanephosphonic acid/2-methyl-2'-acrylamido propane sulfonic acid multipolymer.
9. the circulating water treatment method according to any one of claim 1-5, is characterized in that described copper material corrosion inhibitor is methyl benzotriazazole, benzotriazole or mercaptobenzothiazole.
10. the circulating water treatment method according to any one of claim 1-5, is characterized in that described zinc salt is zinc sulfate or zinc chloride.
11. circulating water treatment methods according to any one of claim 1-5, is characterized in that described long-chain alkyl aryl sulfonate is selected from long-chain alkyl benzene sulfonate.
12. circulating water treatment methods according to claim 11, is characterized in that described long-chain alkyl aryl sulfonate is selected from C
12~ C
18sodium alkyl benzene sulfonate.
13. circulating water treatment methods according to claim 12, is characterized in that described long-chain alkyl aryl sulfonate is selected from Sodium dodecylbenzene sulfonate, tetradecyl benzene sulfonic acid sodium salt and cetyl benzenesulfonic acid sodium.
14. circulating water treatment methods according to any one of claim 1-5, it is characterized in that relative to the effective concentration of each component in pending aqueous solution total amount anti-incrustation corrosion inhibitor be: organic phospho acid 2-15mg/L, organic carboxyl acid base polymer concentration is 2-15mg/L, the effective concentration of copper material corrosion inhibitor is 0.5-1.5mg/L, and the effective concentration of zinc salt is with Zn
2+count 0.5-3.0mg/L.
15. circulating water treatment methods according to any one of claim 1-5, it is characterized in that relative to pending aqueous solution total amount, total effective concentration of long-chain alkyl aryl sulfosalt surfactant is 2-50mg/L.
16. circulating water treatment methods according to claim 6, is characterized in that relative to pending aqueous solution total amount, and total effective concentration of long-chain alkyl aryl sulfosalt surfactant is 2-50mg/L.
17. circulating water treatment methods according to claim 7, is characterized in that relative to pending aqueous solution total amount, and total effective concentration of long-chain alkyl aryl sulfosalt surfactant is 2-50mg/L.
18. circulating water treatment methods according to claim 8, is characterized in that relative to pending aqueous solution total amount, and total effective concentration of long-chain alkyl aryl sulfosalt surfactant is 2-50mg/L.
19. circulating water treatment methods according to claim 9, is characterized in that relative to pending aqueous solution total amount, and total effective concentration of long-chain alkyl aryl sulfosalt surfactant is 2-50mg/L.
20. circulating water treatment methods according to claim 10, is characterized in that relative to pending aqueous solution total amount, and total effective concentration of long-chain alkyl aryl sulfosalt surfactant is 2-50mg/L.
21. circulating water treatment methods according to claim 11, is characterized in that relative to pending aqueous solution total amount, and total effective concentration of long-chain alkyl aryl sulfosalt surfactant is 2-50mg/L.
22. circulating water treatment methods according to claim 12, is characterized in that relative to pending aqueous solution total amount, and total effective concentration of long-chain alkyl aryl sulfosalt surfactant is 2-50mg/L.
23. circulating water treatment methods according to claim 13, is characterized in that relative to pending aqueous solution total amount, and total effective concentration of long-chain alkyl aryl sulfosalt surfactant is 2-50mg/L.
24. circulating water treatment methods according to claim 14, is characterized in that relative to pending aqueous solution total amount, and total effective concentration of long-chain alkyl aryl sulfosalt surfactant is 2-50mg/L.
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| CN103663848B (en) * | 2012-09-10 | 2014-12-03 | 中国石油化工股份有限公司 | Treatment method oil recovery re-injection water |
| CN102989727B (en) * | 2012-11-01 | 2015-02-18 | 广州市金润环保科技有限公司 | Cleaning and sterilizing method of circulating water system, and bactericide |
| CN103304044B (en) * | 2013-06-07 | 2014-05-07 | 中国海洋石油总公司 | Technique for cyclic treatment of coal gasification slag water |
| CN104629958B (en) * | 2013-11-11 | 2018-03-02 | 中国石油化工股份有限公司 | One kind peels off cleansing composition and its application method |
| CN104629917B (en) * | 2013-11-11 | 2017-11-07 | 中国石油化工股份有限公司 | The method of biological clay in a kind of biological clay remover and strip cycles cooling water system |
| CN103739093B (en) * | 2014-01-03 | 2016-03-09 | 广州市特种承压设备检测研究院 | For the Ternary polymerization type corrosion inhibiting and descaling agent and preparation method thereof of central air-conditioning recirculated cooling water |
| CN104261577B (en) * | 2014-10-15 | 2016-03-30 | 河北协同环保科技股份有限公司 | Ash water dispersant and compound method and purposes |
| CN104925964B (en) * | 2015-05-20 | 2017-06-20 | 佛山市南海区巨人化学品制造有限公司 | Eliminating sludge in pipe agent and preparation method thereof |
| CN104944599A (en) * | 2015-07-07 | 2015-09-30 | 傅宇晓 | Environment-friendly cooling water treating agent |
| CN105130022A (en) * | 2015-09-07 | 2015-12-09 | 山东天庆科技发展有限公司 | Preparation method for reverse-osmosis scale inhibition dispersion agent |
| CN106630184A (en) * | 2016-11-25 | 2017-05-10 | 南宁市黑晶信息技术有限公司 | Compound sewage treating agent for treating oilfield sewage and preparation method thereof |
| CN112521950A (en) * | 2019-09-17 | 2021-03-19 | 中国石油化工股份有限公司 | Soil washing composition containing phosphono carboxylic acid, application thereof and method for repairing heavy metal soil |
| CN113880268A (en) * | 2021-09-24 | 2022-01-04 | 广东能源茂名热电厂有限公司 | Sterilization and algae removal treatment method for cooling water of thermal power plant |
| CN115746814A (en) * | 2022-11-16 | 2023-03-07 | 河南海纳石油工程技术有限公司 | Efficient environment-friendly blocking remover |
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